Emulsions

ABSTRACT

Stabilised emulsions in halogenated hydrocarbon solvents of aqueous solutions or dispersions of dyestuffs or textile finishing agents, in which the emulsifying agents present comprise ethyl hydroxyethyl cellulose and one or more anionic surface-active agents. Also treatment of textile materials with such stabilised emulsions.

United States Patent 1191 Jones Nov. 13, 1973 [54] EMULSIONS 3,057,67410/1962 Musser et al. 8/83 3,524,718 8 1970 N d t 8 l [75] Invent: IdaMay Jones Manchester 2,907,624 10/1959 21 243 England 2,971,458 2/1961Kumins et a1 101/170 [73] Assignee: Imperial Chemical Industries LimitedLondon England .Primary ExaminerLeon D. Rosdol [22] Filed; 30 1971Assistant Examiner-T. J Herbert, Jr.

Appl. No.: 139,275

Foreign Application Priority Data May 5, 1970 Great Britain 21,618/70References Cited UNITED STATES PATENTS 3/1958 Sertorio 8/62Attorney-Cushman, Darby and Cushman [5 7] ABSTRACT Stabilised emulsionsin halogenated hydrocarbon solvents of aqueous solutions or dispersionsof dyestuffs or textile finishing agents, in which the emulsifyingagents present comprise ethyl hydroxyethyl cellulose and one or moreanionic surface-active agents. Also treatment of textile materials withsuch stabilised emulsions.

4 Claims, No Drawings EMULSIONS This invention relates to improvedemulsions in halogenated hydrocarbon solvents of dyestuffs and textilefinishing agents, and to the use of such emulsions in the dyeing andfinishing of textile fabrics. v

. It is known to apply dyestuffs and finishing agents to textilematerials with the aid of organic solvents, such as halogenatedhydrocarbons. Such methods of application have been developed as analternative to the conventional procedures utilising aqueous media, forreasons of economy, conservation of water supplies or avoidance ofeffluent problems. The range of dyestuffs or finishing agents which areadequately soluble in such solvents is, however, limited, and it isusually necessary to employ the dyestuff or finishing agent in the formof a dispersion or emulsion in the solvent. One method of obtaining suchdispersions or emulsions which has been proposed consists in preparingan aqueous solution or dispersion in the organic solvent with the aid ofa suitable emulsifying agent.

It has now been found that a combination of ethyl hydroxyethyl cellulosewith an anionic surface-active agent is of particular value for use assuch an emulsifying agent.

According to the present invention there is provided a stabilisedemulsion in a halogenated hydrocarbon solvent of an aqueous solution oran aqueous dispersion of a dyestuff or a textile finishing agent,characterised in that the emulsion contains as emulsifying agents ethylhydroxyethyl cellulose and at least one anionic surface active agent.

By ethyl hydroxyethyl cellulose is meant a mixed cellulose ether whichis prepared by a process involving the following three reactions l.alkali cellulose formation in which cellulose is swollen by aqueoussodium hydroxide; Cell OH 1+ NaOl-l Cell OI-l.NaOl-l;

2. reaction of cellulose. with ethylene oxide in the presence of alkaliCell OH Cell 1- a,.

been converted to ethyl ether groups, or ethoxyethyl ether groups. Ethylhydroxyethyl cellulose is available commercially in a number ofdifferent grades depending on its molecular weight. These grades may becharacterised by their solution viscosities, ranging from to 250 cp. asmeasured on a 5% solution by weight of the ethylhydroxyethyl cellulosein a mixture of 80 20 cially as Turkey RedOil, salts of sulphated methyloleate, salts of dodecylbenzene sulphonic acid, salts of oleic acid andlinoleic acid, salts of tall oil, salts of sulphated mixtures of oleyland cetyl alcohols and salts of oleyl-p-anisidide sulphonic acid andoleyl sarcoside, more particularly the sodium salts thereof. Either asingle anionic surface active agent or a mixture of two or (by weight)toluene/ethanol. Any grade of ethyl hy- I droxyethyl cellulose issuitable for use in the emulsions of the present invention, but thegrade having a solution viscosity as hereinbefore-defined of 20 35 cp ispreferred.

Anionic surface active agents which are suitable for use in theemulsions of the invention include salts of sulphonated castor oil,known collectively commermore such agents may be employed.

Halogenated hydrocarbon solvents which may be employed in the emulsionsof the invention include trichloroethylene, perchloroethylene, l l l:Trichloroethane, carbon tetrachloride, chloroform, monochlorobenzeneand l :2 4-trichlor0benzene.

Dyestuffs which may be incorporated in the emulsions of the inventioninclude any of the well-known classes, for example acid, basic, direct,reactive or disperse dyestuffs as conventionally employed for the dyeingof textile materials composed of polyamide, cotton, wool, silk, acetate,polyester, viscose or acrylic fibres or filaments.

Textile finishing agents which may be incorporated in the emulsions ofthe invention include fluorescent optical brightening agents, such asthe sodium salts of bis-triazinyl-aminostilbene di-sulphonic acids,waterproofing agents such as stearamidomethylpyridinium chloride andN-methylolstearamide, crease-resist resins such asdimethyloldihydroxy-ethylene urea, antistatic and antisoil/soil releaseagents such as condensates of ethylene oxide with polyamides,crystallisable polyesters containing polyoxyalkylene groups, for examplepolyoxyalkylene terephthalate/polyalkylene terephthalate blockcopolymers and copolymers of polymerisable acids, for example acrylicacid, with other polymerisable vinyl monomers, softening agents such asfatty quaternary ammonium salts, desizing agents such as enzymepreparations, flameproofing or flame retarding agents such as antimonytrioxide or mixtures of boric acid and borax. I

The emulsions of the present invention may be produced by subjectinga'mixture' of a halogenated hydrocarbon solvent and an aqueous solutionor dispersion of a dyestuff of textile finishing agent to suitablemechanical agitation in the presence of ethyl hydroxyethyl cellulose andat least one anionicsurface-active agent.

The'emulsifying agents used, that is to say the ethyl hydroxyethylcellulose and the anionic'agent or agents, maybe initially present ineither the halogenated hydrocarbon solvent or the aqueous solution ordispersion of the dyestuff or finishing agent, or both. However, havingregard to the solubility properties of ethylhydroxyethylcellulose,inparticular the 20 35 cp. I grade which ispreferred for use in-the present invention, it will usually beconvenient for this constituent to be dissolved initially in-thehalogenated hydrocarbon solvent. The anionic agent or agents may bedissolved initially in either the solvent phase or the aqueous phase,but if desired, in accordance with a well-known technique ofemulsification using such agents, it may be produced in situ by reactionbetween a suitable organic acid precursor, for exampledodecylbenzene-sulphonic acid, dissolved in the halogenated hydrocarbonsolvent phase and an alkali, for example sodium hydroxide, dissolved inthe aqueous phase.

The relative proportions of the halogenated hydrocarbon solvent and theaqueous phase incorporated in i the emulsions of the invention may varywidely, according to the manner in which the emulsions are to be appliedto the textile fabric and to the type and solubility of the dyestuffs orfinishing agents employed. Commonly, however, the amount of water willlie in the range 0.3 to 20.0% of the total weight of the emulsion.

The emulsions of the present invention are valuable for the applicationto textile materials of the dyestuffs or finishing agents which theycontain. In general, the emulsions may be applied to the textilematerials by passing, exhaustion or any other conventional form ofimpregnation, followed by evaporation of the halogenated hydrocarbonsolvent and, if necessary, a final baking operation to fix the dyestuffor finishing agent on the textile material. The halogenated hydrocarbonsolvent which is evaporated during this process may, of course, berecovered for re-use.

Textile materials to which the emulsions of the invention may be appliedinclude yarns and knitted, woven or non-woven fabrics.

The use of the emulsions of the invention instead of conventionalaqueous solutions or dispersions of dyestuffs or textile finishingagents confers a number of advantages. Exhaustion may be more rapid inbatchwise processes and wetting out easier and pick-up better in paddingprocedures. Losses in dimensional stability are reduced. The halogenatedhydrocarbon solvents have lower specific heats and latent heats ofevaporation than water, thus reducing costs of heating and drying andalso permitting economic recovery of the organic liquid for reuse whichavoids the increasingly severe difficulties being met in the treatmentof aqueous effluents. A number of finishing treatments, and also drycleaning of textile materials, are carried out in nonaqueous media andin suitable cases these may be combined with application of a treatingagent to the textile material.

Of particular advantage for such applications is the excellent stabilityof the emulsions of the invention; these show no detectable separationof the organic and aqueous phases over a period of. several days. Incontrast, emulsions of similar composition but containing only the ethylhydroxyethyl cellulose' as stabiliser, that is to say omitting theanionic surface active agent or agents, show appreciable separationafter as little as one day. lnferior results are also obtained by use ofan anionic agent along (i.e., omitting the ethyl hydroxyethylcellulose); it is possible to achieve a moderate degree of stability ofthe emulsions by increasing the concentration of the anionic agent, butthis frequently has an adverse effect on the subsequent use of theemulsion where certain types of dyestuff are involved.

The invention is illustrated but not limited by the following examplesin which all parts and percentages are by weight unless otherwisestated: Example 1 0.70 Part of the dyestuff which is the disodium saltof 2-[2'-acetylamino-4-(4 -chloro-6 '-amino-1 :3" 5 -triazine-2-ylamino)phenylazo naphthalene-4: 8- disulphonic acid and 022 part ofsoda ash are dissolved in 13.3 parts of water, and 1.5 parts of TurkeyRed Oil isthen added and stirred until in solution. 1.5 Parts of ethylhydroxyethyl cellulose of viscosity 20-35 cp (measured at 25 C on a 5 kbyweight solution'in 80:20 toluene/ethanol) is dissolved in 132 parts ofperchloroethylene and is stirred at high speed while the solution ofdyestuff is slowly added over 5 minutes. High speed stirring iscontinued for a further 5 minutes, followed by slow stirring for 2minutes to allow entrapped air to escape. The resulting emulsion hasexcellent stability.

A sample of cellulosic textile material is padded in the emulsion, driedand baked at 200 C for 1 minute. The textile material is thereby evenlydyed a yellow colour.

If the above procedure is followed but omitting the Turkey Red Oil andincreasing the amount of ethyl hydroxyethyl cellulose from 1.5 parts to2.25 parts, the resulting emulsion is found to have considerablyinferior stability, separation of aqueous phase being detectable after18 20 hours, whereas the emulsion obtained using bothethylhydroxyethylcellulose and Turkey Red Oil shows no separation for atleast 10 days.

If the procedure first described above is followed but omitting theethyl hydroxyethyl cellulose and increasing the amount of Turkey Red Oilfrom 1.5 parts to 3 parts, a good emulsion is initially obtained butthis shows separation of the aqueous phase after 3 days. Example 2 Theprocedure of Example 1 is repeated, except that in place of the dyestuffthere described there is. used 1.1parts of the dyestuff which is thetri-sodium salt of copper phthalocyanine-3-(sulphonic acid):;-3{N- [,8-6chloro-4'-methoxyl :3 15-triazin-2-ylamino)ethyl sulphonamide}.

Cellulose textile material treated with the stable emulsion so obtainedis evenly dyed a turquoise colour. Example 3 The procedure of Example 1is repeated, except that is place of. the dyestuff there described thereis used 0.75 part of the dyestuff which is the tetrasodium salt of1-{2:5-dimethyl-4-[4"-(4-chloro- 6"-amino-l 23135;"triazin-2-ylamino)7-sulphonaphth- 1 -ylazo]phenylazo} naphthalene-2 5.7-trisulphonic acid.

Cellulosic material treatedwith the resulting stable emulsion is evenlydyed an orange-brown colour. Example 4 The procedure described inExample 1 is repeated, except that the perchloroethylene is replaced byan equal weight of 1 1 l-trichloroethane. An emulsion of excellentstability is again obtained. Example 5 The procedure described inExample 1 is repeated,

except that the perchloroethylene is replaced by an equal weight oftrichloroethylene. An emulsion of excellent stability is obtained.Example 6.

1.4 parts of the dyestuff described in Example 1 and 0.45 part of sodaash are dissolved in 26.6 parts of water. 1.5 parts of ethylhydroxyethyl cellulose of viscosity 20-36cp, measured as described inExample 1, is dissolved in 132 parts of perchloroethylene and 1.0 partof tall oil is added, followed by 0.5 part of triethanolamine. Thesolution is stirred athigh speed whilst the dyestuff solution is addeddropwise as quickly as practicable/High speed stirring is continued for5 minutes, followed by slow stirring for 2 minutes to allow de-aerationto take place. The resulting emulsion has excellent stability and may beemployed for thecontinuous dyeing of cellulose textile materialsaccording to the procedure described in Example 1. Example 7 i 0.05 partof the dyestuff which is the pentasodium salt of1-(2'-methyl-3-[4-chloro-6"-sulphoanilino- 1" :3 :5-triazin-2"-ylamino]-5 '-sulphophenyl) -3- carboxy-4-[2"-sulpho-4-(chlor'osulphoanilino-1 3":5-triazin-2"-ylamino)phenylazo]-5-pyrazolone and 1.1 parts of urea aredissolved in 1.9 parts of water; 0.145 part of a 45% aqueous solution ofthe sodium salt of sulphated methyl oleate and 0.26 part of sodiumdodecylbenzene sulphonate are then stirred in until dissolved. Thissolution is added to a solution of 0.025 part of ethyl hydroxyethylcellulose of viscosity -35 cp, measured as described in Example 1, inparts of perchloroethylene and mixed 26 give a coarse emulsion. Thisemulsion is gradually diluted with a further 164 parts ofperchloroethylene to form a stable product. I

Cellulosic textile material is batchwise dyed a yellow colour byimmersion in a dyebath consisting of the above-described emulsion whichis continuously agitated and gradually heated to boiling point,.thenmaintained at the boil for minutes. Example 8 0.036 Part of the dyestuffidentified in the Colour Index as C.l. Acid Yellow 72 is dissolved in0.6 part of water, and 0.145 part of a 45% aqueous solution of thesodium salt of sulphated methyl oleate is added. The dyestuff solutionso obtained is added with good agitation to a solution of 0.025 part ofethyl hydroxyethyl cellulose of viscosity 2035 cp. in IS parts ofperchloroethylene; the emulsion so formed is added with stirring to 149parts of perchloroethylene at 30 C, to yield a stable product.

The resulting emulsion is used for the batchwise dye ing of nylontextile materials to a yellow colour by immersing the textile materialin the emulsion when maintained at 85 C, at which temperature a clearsolution is formed.

Example 9 The pro cedure of Example 8 is place of the dyestuff theredescribed 0.016 part of the dyestuff which is identified in the ColourIndex as C.l. Acid Red 266. A similar result is obtained. Example 10 Theprocedure of Example 8 is repeated, using in place of the dyestuff theredescribed 0.015 part of the dyestuff 4-[4-(phenylazo)phenylazo]N-ethy1-N-(msulphobenzyl)aniline. A similar result is obtained. Example11 0.02 Part of the dyestuff identified in the Colour Index as C.l. AcidBlue 67 is dissolved in 0.6 part of water, and 0.045 part ofdodecylbenzene sulphonic acid added. The solution so obtained is addedwith good agitation to a solution of 0.025 parts of ethyl hydroxyethylcellulose of viscosity 20-35cp, in 15 parts of perchloroethylene; theemulsion so formedis added with stirring to a further 145 parts ofperchloroethylene at 30 C.

The resultant dye liquor is employed for the batchwise dyeing of nylontextile material according to the following procedure Perchloroethyleneis circulated through the nylon textile material at 40 C for 10 minutes;the dye liquor in an amount sufficient to deposit from 1.25 to 1.5 byweight of the dyestuff (based on the textile material taken), is thencirculated through the material so treated at'40 C for 15 minutes, afterwhich the temperature is raised to 85 C over a period of 40 minutes andthen maintained at that value for 15 minutes. The material is dried at70-80 C. Example 12 repeated, using in The procedure of Example 11 isrepeated, using in place of the dyestuff there identified 0.016 part ofthe dyestuff referred to in Example 10. A similar result to thatdescribed in Example 1 1 is obtained. Example 13 Thqprocedure of Example11 is repeated, using in place of the dyestuff there identifed 0.037part of the dyestuff identified in the Colour Index as C.l. Acid Yellow135. A similar result is obtained.

' Example 14 The procedure of Exa mple 11 is repeated, using in place ofthe dyestuff there identified 0.017 part of the dyestuff identified inthe Colour Index as C.l. Acid Blue 40. A similar result is obtained.

Example 15 The procedure of Example 11 is repeated, using in place ofthe dyestuff there identified 0.036 part of the dyestuff identified inthe Colour index as C.l. Acid Yellow 72. A similar result is obtained.

Example 16 1 part of Turkey Red Oil is dissolved in 30 parts of an 18solution in aqueous diethylene glycol of a fluorescent brightening agentwhich is an anionic stilbene derivative; this solution is added to asolution of 5 parts of ethyl hydroxyethyl cellulose, viscosity 20 35cp., in 70 parts of per chloroethylene, whilst the latter is agitatedwith a Silverson homogeniser. Agitation is continued for 1 minute afterthe addition'is complete. The resultant emulsion is viscous butpourable, and has excellent stability. It is suitable for the opticalbleaching of cellulosic of polyamide fabrics and for this purpose it maybe diluted with additional perchloroethylene without breakage of theemulsion occurring.

In a typical treatment, the diluted emulsion is padded on to acellulosic fabric so as to deposit 0.05-0.5% by weight of thefluorescent brightening agent on the fabric; the solvent is then removedby passing the fabric through a steam chamber and the fabric is dried atC for 5 minutes' The treated fabric is considerably brighter inappearance than the untreated fabric.

Example 17 v I '1 part of Turkey Red Oil is dissolved in 30 parts of a50 aqueous solution of dimethyloldihydroxyethy lene urea and is added toa solution of 1.5 parts of ethyl hydroxyethyl cellulose, viscosity 2035cp., in parts of perchloroethylene whilst the latter is agitated with aSilverson homogeniser. Agitation is continued for 1 minute after theaddition is complete. The resultant emulsion, which is viscous butpourable, has excellent stability. It is suitable for applicationtogether with a latent acid catalyst to cellulosicand'polyester/cellulosic fabrics for the production of crease-resist anddurable press finishes, and for. this purpose it may be diluted withadditional perchloroethylene without the emulsion breaking.

In a typical treatment, a latent acid catalystsu'ch as monochloroaceticacid or stearamidomethylpyridinium chloride is added to the dilutedperchloroethylene emulsion and the resulting composition is'padded on tocellulosic or polyester-cellulosic blend fabric so as to deposit 4 8 byweight of the dimethylol dihydroxyethylene urea on the fabric. Thesolvent is then removed by passing the fabric through a steam chamher,the fabric is thereafter'dried at 60 C for 5 minutes and then heated ata temperature of C for 3 minutes.

The treated fabric possesses much improved wet and dry crease recoveryproperties compared with the untreated fabric.

Example 18 0.4 part of sodium hydroxide is dissolved in 50 parts of a 15w/v. aqueous dispersion of a polyethylene terephthalate/polyoxyethyleneterephthalate block copolymer; 2 parts of ethyl hydroxyethyl cellulose,viscosity 20 35 cp., are dissolved in 45 parts of perchloroethylene,followed by 2.6 parts of oleic acid. The aqueous dispersion is addedover a period of minutes to the oil phase, using a high-speed stirrer;after the addition is completed, stirring is continued at high speed for3 minutes, followed by slow-speed stirring for 2 minutes. The resultingemulsion has excellent stability and is suitable for conferring durableantistatic and anti-soil effects on polyester, polyester/cellulosic andpolyester/wool blend fabrics; it may be diluted for this pur pose withadditional perchloroethylene without the emulsion breaking.

The diluted emulsion is padded on to polyester fabric so as to deposit 13 by weight of the polyethylene terephthalate/polyoxyethyleneterephthalate block copolymer on to the fabric. The fabric is dried byheating at 70 C for 20 minutes. The treated fabric is found to possesssuperior antisoil-redeposition, stain release and antisoil properties tothe untreated fabric.

Example 19 0.2 Part of an azo dye, prepared by coupling 4- aminobenzenesulphona mide on to N-methyl-N-B- cyanoethyl aniline, and 0.1 part ofthe polyurea deflocculating agent obtained as described below from mixed2,4- and 2,6-tolylene diisocyanates and afatty secondary amine derivedfrom soya are gravel milled in 3 parts of perchloroethylene for 40hours. The resulting dispersion is added with stirring to a solution of1 part ethyl hydroxyethyl cellulose of viscosity 20-35 cp (measured at25 C on a 5 by weight solution in 80:20 toluene/ethanol) dissolved in115 parts perchloroethylene. A mixture of 5 parts of water and 1 part ofcially available 40 solution in butyl acetate of polymerised mixed 2,4-and 2,6-tolylene diisocyanates con taining 5.7 of isocyanate groups andless than 0.5 of free tolylene diisocyanate is gradually added to astirred solution in 1 18 parts of acetone at 50-55 C of 53.5 parts of afatty secondary amine derived from soya, commercially available underthe trade name Armeen 2S (Armeen is a Registered Trade Mark). Theacetone is then removed by distillation up to a temperature of C underreduced pressure.

Example 20 0.5 Parts of the dye identified in the Colour Index as ClBasic Red 18 is dissolved in 5 parts boiling water and 5 parts TurkeyRed Oil are added. The dye solution so obtained is added with goodagitation to a solution of 1 part of ethyl hydroxyethyl cellulose o f20-35 cp. in 115 parts perchloroethylene and the emulsion so formed isdiluted with stirring with 687 parts perchloroethylene.

The resulting emulsion is used for the batchwise dyeing ofpolyacrylonitrile textile materials to a red colour by immersing thetextile material in the emulsion for 30 minutes at C in a closed vesselwith continuous agitation.

We claim:

1; .A stabilized emulsion in a halogenated hydrocarbon solvent of anaqueous preparation of a textile treatment agent selected from dyestuffsand finishing agents, wherein there are present as emulsifying agents asethyl hydroxyethyl cellulose having a solution viscosity, measured on a5% solution by weightin 80:20 (by weight) toluene/ethanol of from 20 to35 cp, and at least one anionic surface-active agent, the amount ofwater present in said emulsion being from 0.3 to 20% of the total weightof the emulsion.

2. A stabilised emulsion as claimed in claim 1, wherein the anionicsurface-active agent is selected from salts of sulphonated castor oil,the triethanolamine salt of tall oil, the sodium salt of sulphatedmethyl oleate, sodium dodecylbenzenesulphonate and sodium oleate. g

3. A stabilised emulsion as claimed in claim 1, wherein the halogenatedhydrocarbon solvent is selected from perchloroethylene,trichloroethylene and l :1 1-trich1oroethaiie.-

4. A process for the treatment of textile materials in which there isapplied to the textile material a stabilised emulsion as claimed inclaim 1 and the material is thereafter treated in known manner to fixthe treatment agent thereupon.

2. A stabilised emulsion as claimed in claim 1, wherein the anionicsurface-active agent is selected from salts of sulphonated castor oil,the triethanolamine salt of tall oil, the sodium salt of sulphatedmethyl oleate, sodium dodecylbenzenesulphonate and sodium oleate.
 3. Astabilised emulsion as claimed in claim 1, wherein the halogenatedhydrocarbon solvent is selected from perchloroethylene,trichloroethylene and 1:1:1-trichloroethane.
 4. A process for thetreatment of textile materials in which there is applied to the textilematerial a stabilised emulsion as claimed in claim 1 and the material isthereafter treated in known manner to fix the treatment agent thereupon.